JPS62220932A - Electrochromic display element - Google Patents
Electrochromic display elementInfo
- Publication number
- JPS62220932A JPS62220932A JP61063775A JP6377586A JPS62220932A JP S62220932 A JPS62220932 A JP S62220932A JP 61063775 A JP61063775 A JP 61063775A JP 6377586 A JP6377586 A JP 6377586A JP S62220932 A JPS62220932 A JP S62220932A
- Authority
- JP
- Japan
- Prior art keywords
- display
- transparent plate
- substrate
- display element
- adhesive layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000758 substrate Substances 0.000 claims abstract description 34
- 239000012790 adhesive layer Substances 0.000 claims abstract description 19
- 239000003792 electrolyte Substances 0.000 claims description 8
- 229920002845 Poly(methacrylic acid) Polymers 0.000 claims description 5
- 125000005907 alkyl ester group Chemical group 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 9
- 239000011521 glass Substances 0.000 abstract description 9
- 229920005989 resin Polymers 0.000 abstract description 9
- 239000011347 resin Substances 0.000 abstract description 9
- 125000000217 alkyl group Chemical group 0.000 abstract description 3
- -1 acrylate ester Chemical class 0.000 abstract description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 abstract 1
- 230000003247 decreasing effect Effects 0.000 abstract 1
- 239000000853 adhesive Substances 0.000 description 24
- 230000001070 adhesive effect Effects 0.000 description 24
- 239000010410 layer Substances 0.000 description 18
- 239000000463 material Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 13
- 239000007772 electrode material Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 5
- 230000006866 deterioration Effects 0.000 description 4
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 4
- 229910001930 tungsten oxide Inorganic materials 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000001723 curing Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 229910003437 indium oxide Inorganic materials 0.000 description 3
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 238000007650 screen-printing Methods 0.000 description 3
- 125000006850 spacer group Chemical group 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- SSWAPIFTNSBXIS-UHFFFAOYSA-N dioxido(dioxo)tungsten;iron(2+) Chemical compound [Fe+2].[O-][W]([O-])(=O)=O SSWAPIFTNSBXIS-UHFFFAOYSA-N 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- QCTJRYGLPAFRMS-UHFFFAOYSA-N prop-2-enoic acid;1,3,5-triazine-2,4,6-triamine Chemical compound OC(=O)C=C.NC1=NC(N)=NC(N)=N1 QCTJRYGLPAFRMS-UHFFFAOYSA-N 0.000 description 2
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002482 conductive additive Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
この発明は、表示極のエレクトロクロミック物質と対向
極の対極物質との電解液を介した反応物質の着色変化に
よって文字や模様などを表示するエレクトロクロミック
表示素子に関する。[Detailed Description of the Invention] [Industrial Application Field] This invention displays characters, patterns, etc. by color change of a reactant between an electrochromic material of a display electrode and a counter electrode material of a counter electrode through an electrolyte. The present invention relates to an electrochromic display element.
この種表示素子の代表的なものとして、たとえば第２図
に示すように、透光性である表示側基板１の内面に透明
電極２を介してエレクトロクロミック物質層３を設けて
所要パターンを構成するセグメントに分画された表示極
４とし、対向側基板５の内面に電極６を介して対極物質
層７を設けて対向極８とし、対向配置された側基板１．
５の両極４．８間に電解液９を封入した素子２００があ
る。なお、図中の１０は表示極４の各セグメント間に介
在する絶縁保護膜、１１は対極物質層７上に設けられた
背景材、１２は側基板１．５間に介在させたスペーサ、
１３はリード端子、１，４は電極６と対向極側のリード
端子１３とを電気的に接続する導電層である（文献不詳
）。As a typical display element of this kind, as shown in FIG. 2, for example, an electrochromic material layer 3 is provided on the inner surface of a transparent display substrate 1 via a transparent electrode 2 to form a desired pattern. A display electrode 4 is divided into segments, a counter electrode material layer 7 is provided on the inner surface of a counter substrate 5 via an electrode 6 to serve as a counter electrode 8, and side substrates 1.
There is an element 200 in which an electrolytic solution 9 is sealed between the two electrodes 4 and 8 of the device. In addition, 10 in the figure is an insulating protective film interposed between each segment of the display electrode 4, 11 is a background material provided on the counter electrode material layer 7, 12 is a spacer interposed between the side substrates 1.5,
13 is a lead terminal, and 1 and 4 are conductive layers that electrically connect the electrode 6 and the lead terminal 13 on the opposite electrode side (document unknown).
この場合、対向極８を共通電極として所要の表示極４に
電圧を印加することにより、エレクトロクロミック物質
と対極物質との電解液９を介した反応物質の着色変化、
たとえばエレクトロクロミック物質が酸化タングステン
で電解液がリチウム塩を電解質とするものであるとき、
の反応による着色変化にて所要パターンの表示がなされ
る。In this case, by applying a voltage to the required display electrodes 4 using the counter electrode 8 as a common electrode, color change of the reactant between the electrochromic substance and the counter electrode substance via the electrolyte 9;
For example, when the electrochromic material is tungsten oxide and the electrolyte is a lithium salt electrolyte, the desired pattern is displayed by the color change caused by the reaction.
ところで、たとえば第３図のようにこのような表示素子
２００を複数個配列した表示ボード１５や表示素子２０
０自体が比較的大きいディスプレイでは、一般に外観向
上のためにエスカッションと称される不透明な外枠１６
によって表示素子２００の周辺部、つまりリード端子１
３部分ならびに前景色と色調の異なるスペーサ１２部分
を外部から遮蔽して表示領域Ａのみを露呈させている（
文献不詳）。By the way, for example, as shown in FIG.
0 itself is relatively large, an opaque outer frame 16 called an escutcheon is generally used to improve the appearance.
The periphery of the display element 200, that is, the lead terminal 1
3 portions and the spacer 12 portions having different foreground colors and tones are shielded from the outside to expose only the display area A (
(Reference unknown).
しかしながら、上記外枠１６を用いた場合、表示面つま
り表示側基板１の表面が外枠１６の表面よりも奥まった
位置にあることから、表示全体が視覚的に窮屈であり、
とくに第２図の矢印ｔで示すように表示に対する照明光
の入射方向または視線方向が斜めになると外枠１６によ
って影または死角になる領域Ｂを生じて表示の視認性が
悪いという問題があった。However, when the outer frame 16 is used, the display surface, that is, the surface of the display-side substrate 1 is located at a deeper position than the surface of the outer frame 16, so the entire display is visually cramped.
Particularly, as shown by arrow t in FIG. 2, if the direction of incidence of illumination light on the display or the direction of line of sight is oblique, there is a problem that the outer frame 16 creates a region B that is a shadow or a blind spot, resulting in poor visibility of the display. .
したがって、この発明は、上記問題点を解決することに
より、表示の視認性にすぐれ、しかも長期の使用によっ
ても表示品質の低下をきたさないエレクトロクロミック
表示素子を提供することを目的としている。Therefore, an object of the present invention is to provide an electrochromic display element that has excellent display visibility and does not cause deterioration in display quality even after long-term use by solving the above-mentioned problems.
この発明者らは、上記目的を達成するために鋭意検討を
重ねた結果、表示側基板の外面に透明板を特定手段で取
付けた場合、該透明板の屈折率効果によって表示がその
表面に浮き出して視認され、もって前記エスカッション
の外枠を用いた場合に影または死角になる領域を生じず
かつ視覚的な窮屈さがなく、しかも表示色および背景色
が阻害されず長期にわたってすぐれた表示品質が維持さ
れることを見い出し、この発明をなすに至った。As a result of intensive studies to achieve the above object, the inventors found that when a transparent plate is attached to the outer surface of the display side substrate by a specific means, the display stands out on the surface due to the refractive index effect of the transparent plate. When the outer frame of the escutcheon is used, there is no shadow or blind spot, there is no visual cramping, and the display color and background color are not obstructed, providing excellent display quality over a long period of time. The inventors have found that this can be maintained, and have come up with this invention.
すなわち、この発明は、少なくとも表示側が透光性であ
る一対の基板が対向配置され、表示側の基板内面に形成
された表示極と対向側の基板内面に形成された対向極と
の間に電解液が封入されてなるエレクトロクロミック表
示素子において、表示側の基板外面に透明板が紫外線に
て硬化されたポリ （メタ）アクリル酸アルキルエステ
ルを主体とする接着剤層を介して接着されていることを
特徴とするエレクトロクロミック表示素子に係る。That is, in the present invention, a pair of substrates whose at least the display side is translucent are placed opposite each other, and electrolysis occurs between the display electrode formed on the inner surface of the substrate on the display side and the counter electrode formed on the inner surface of the substrate on the opposite side. In an electrochromic display element in which a liquid is sealed, a transparent plate is bonded to the outer surface of a substrate on the display side via an adhesive layer mainly made of poly(meth)acrylic acid alkyl ester cured by ultraviolet light. The present invention relates to an electrochromic display element characterized by:
第１図はこの発明に係るエレクトロクロミック表示素子
の構造例を示すものであり、図中の符号１〜１４および
１６は前記第２図における同符号の各部と同一構成であ
る。FIG. 1 shows an example of the structure of an electrochromic display element according to the present invention, and reference numerals 1 to 14 and 16 in the figure have the same structure as each part with the same reference numerals in FIG.
この表示素子１００においては、表示側基板１の外面の
表示領域Ａ部分に、ガラスやポリメチルメタクリレート
の如き（メタ）アクリル酸アルキルエステル系樹脂など
からなる透明板１７が、紫外線にて硬化されたポリ （
メタ）アクリル酸アルキルエステルを主体とする接着剤
層１８を介して背面全面で接着されており、該透明板１
７の表面と外枠１６の表面がほぼ同じ高さとなるように
設定されている。In this display element 100, a transparent plate 17 made of glass or a (meth)acrylic acid alkyl ester resin such as polymethyl methacrylate is hardened with ultraviolet rays in a display area A portion of the outer surface of the display side substrate 1. Poly (
The entire back surface of the transparent plate 1 is bonded via an adhesive layer 18 mainly composed of alkyl meth)acrylate.
7 and the surface of the outer frame 16 are set to be approximately at the same height.
ここで、上記の接着剤層１８は、それ自体の透明性にす
ぐれ、かつ透明板１７ならびに一般にガラスなどからな
る表示側基板ｌと近似した屈折率を有するので両者間で
反射界面を形成せず、また紫外線にて硬化されたもので
あるから溶剤揮発型の接着剤層のように揮発成分による
気泡を含まないという特徴を有している。したがって、
この表示素子１００にあっては、表示および背景の色調
ならびに表示パターンが接着剤層１８にて阻害されず、
しかも透明板１７と表示側基板１とが一体的な透明屈折
層として機能して表示パターンを透明板１７の表面に浮
き出だせることになるため、外枠１６による影や死角が
解消され、表示領域Ａ全体も視覚的に広くとらえられ、
表示の視認性が前記第２図の従来の表示素子に比較して
飛躍的に向上する。Here, the adhesive layer 18 itself has excellent transparency and has a refractive index similar to that of the transparent plate 17 and the display side substrate l, which is generally made of glass, so that no reflective interface is formed between the two. Also, because it is cured with ultraviolet light, it has the characteristic that it does not contain bubbles caused by volatile components, unlike solvent-volatile adhesive layers. therefore,
In this display element 100, the display and background colors and display patterns are not inhibited by the adhesive layer 18;
Moreover, since the transparent plate 17 and the display-side substrate 1 function as an integrated transparent refractive layer and the display pattern can be embossed on the surface of the transparent plate 17, shadows and blind spots caused by the outer frame 16 are eliminated, and the display area The entire A can also be visually captured broadly,
The visibility of the display is dramatically improved compared to the conventional display element shown in FIG.
そして、さらに重要な点は、接着剤層１８が紫外線にて
硬化されたポリ （メタ）アクリル酸アルキルエステル
を主体とするものであるため、該接着剤層１８の耐候性
が極めて良好で長期にわたつて黄変や劣化を生じないこ
とである。すなわち、紫外線硬化型接着剤の樹脂成分と
しては一般にエポキシアクリレート、ポリエステルアク
リレート、ポリウレタンアクリレート、ポリエーテルア
クリレート、メラミンアクリレートなどのオリゴマーを
主体とするものが汎用されているが、これら樹脂成分を
主体とした紫外線硬化型接着剤を透明板１７と表示側基
板１との接着に使用すると後述比較例で示すように経時
的に黄変を生じて表示および背景の色調が阻害されると
いう問題がある。More importantly, since the adhesive layer 18 is mainly made of poly(meth)acrylic acid alkyl ester cured by ultraviolet light, the adhesive layer 18 has extremely good weather resistance and can last for a long time. It must not cause yellowing or deterioration over time. In other words, the resin components of UV-curable adhesives are generally based on oligomers such as epoxy acrylate, polyester acrylate, polyurethane acrylate, polyether acrylate, and melamine acrylate. When an ultraviolet curable adhesive is used to bond the transparent plate 17 and the display-side substrate 1, there is a problem in that it yellows over time, impairing the color tone of the display and background, as shown in the comparative example below.
この発明において、接着剤層１８の形成に使用する紫外
線硬化型接着剤は、つぎの一般式；％式％
で示される（メタ）アクリル酸アルキルエステルを主体
とする硬化性成分と光硬化剤（光重合開始剤）を含むも
のであり、硬化性成分中には必要に応じて上記一般式以
外のモノマーやオリゴマーなどを少量含有していてもよ
い。光硬化剤としては従来より紫外線硬化型接着剤用と
して知られる種々の化合物をいずれも使用可能である。In this invention, the ultraviolet curable adhesive used to form the adhesive layer 18 is composed of a curable component mainly composed of (meth)acrylic acid alkyl ester represented by the following general formula; (photopolymerization initiator), and the curable component may contain a small amount of monomers or oligomers other than those of the above general formula, if necessary. As the photocuring agent, any of the various compounds conventionally known for use in ultraviolet curable adhesives can be used.
また上記−ａ式中のＲで示されるアルキル基としては、
炭素数１〜２０程度のものが好適である。In addition, the alkyl group represented by R in the above formula -a is,
Those having about 1 to 20 carbon atoms are suitable.
一方、第１図の表示素子１００において、上述した透明
板１７および接着剤層１８以外の各部は、従来のエレク
トロクロミック表示素子と同様に構成される。On the other hand, in the display element 100 of FIG. 1, each part other than the above-mentioned transparent plate 17 and adhesive layer 18 is configured in the same manner as a conventional electrochromic display element.
すなわち、両側基板１．５としては一般にガラスなどの
透光性材料が用いられるが、対向側基板５は非透光性で
あっても差し支えない。そして透明電極２は、酸化イン
ジウム、酸化スズなどの透明性導電材料からなり、表示
側基板１の内面に真空蒸着法、スパッタ法、イオンブレ
ーティング法などの既存の薄膜形成技術によって形成さ
れている。また電極６には金、白金の如き貴金属および
これらと他の金属との合金、あるいは透明電極２と同様
の材料が使用され、前記同様の薄膜形成技術のほか、金
属の場合では箔状物を圧着あるいは接着する方法によっ
て対向側基板５の内面に形成される。That is, although a light-transmitting material such as glass is generally used as the both-side substrates 1.5, the opposite-side substrate 5 may be non-light-transmitting. The transparent electrode 2 is made of a transparent conductive material such as indium oxide or tin oxide, and is formed on the inner surface of the display-side substrate 1 using existing thin film forming techniques such as vacuum evaporation, sputtering, and ion blating. . In addition, the electrode 6 is made of noble metals such as gold and platinum, alloys of these and other metals, or the same material as the transparent electrode 2. In addition to the same thin film forming techniques as described above, in the case of metals, foil-like materials are used. It is formed on the inner surface of the opposing substrate 5 by pressure bonding or adhesion.
エレクトロクロミック物質層３、対極物質層７および電
解液９としては、表示色に応じて種々の材料の組み合わ
せが存在する。たとえば、表示色が青色の場合、エレク
トロクロミック物質層３として酸化タングステン（Ｗ
Ｏａ ）が、対極物質層７として酸化タングステン、二
酸化マンガン（Ｍｎｏ、）、タングステン酸鉄ＣＦｅｔ
０３ ・３Ｗ０３）、などが、電解液９としてＬｉ
Ｃ１！０４などのリチウム塩をプロピレンカーボネート
などの非水系溶媒に溶解したものが、代表的に使用され
る。そして、エレクトロクロミック物質層３は前記同様
の薄膜形成技術によって透明電極２上に形成され、対極
物質層９は上記対極物質と結合剤と必要に応じてカーボ
ンブラックなどの導電助剤を含む塗料を電極６上にスク
リーン印刷法などで塗布硬化して形成される。There are various combinations of materials for the electrochromic material layer 3, counter electrode material layer 7, and electrolyte 9 depending on the display color. For example, when the display color is blue, the electrochromic material layer 3 is tungsten oxide (W).
Oa ) is made of tungsten oxide, manganese dioxide (Mno, ), iron tungstate CFet as the counter electrode material layer 7.
03 ・3W03), etc. are used as the electrolyte 9.
A lithium salt such as C1!04 dissolved in a non-aqueous solvent such as propylene carbonate is typically used. Then, the electrochromic material layer 3 is formed on the transparent electrode 2 by the same thin film forming technique as described above, and the counter electrode material layer 9 is made of a paint containing the above-mentioned counter electrode material, a binder, and, if necessary, a conductive additive such as carbon black. It is formed by coating and curing on the electrode 6 using a screen printing method or the like.
また背景材１１は、対向極８を隠蔽してそれ自身の色調
を表示の背景とするものであり、たとえば白色の場合で
は二酸化チタンと電解液のゲル体などが使用され、対極
物質層７と同様にスクリーン印刷法などで塗布形成され
る。さらに絶縁保護膜１０としては５ｉＯｚが、導電層
１４としては銀ペーストなどが、それぞれ使用される。The background material 11 hides the counter electrode 8 and uses its own color tone as the display background. For example, in the case of white, a gel of titanium dioxide and an electrolyte is used, and the counter electrode material layer 7 and Similarly, it is formed by coating using a screen printing method or the like. Furthermore, 5 iOz is used as the insulating protective film 10, and silver paste or the like is used as the conductive layer 14.
この発明のエレクトロクロミック表示素子は、表示側の
基板外面に透明板が紫外線にて硬化されたポリ （メタ
）アクリル酸アルキルエステルを主体とする接着剤層を
介して接着されたものであり、表示パターンが屈折率効
果によって上記透明板の表面に浮き出して視認されるた
め、素子表面の周辺部をエスカッションと称される外枠
で隠蔽しても影や死角を生じず、かつ表示領域全体も視
覚的に広くとらえられ、上記透明板を設けていない従来
の表示素子に比較して表示の視認性が飛曜的に向上する
。また、この表示素子における上記接着剤層は、透明性
が良好でかつ気泡を含まないため表示および背景の色調
および表示パターンを阻害せず、しかも極めてすぐれた
耐候性を備えて経時的に黄変や劣化を生じないので表示
品質を長期にわたって良好に維持させる。The electrochromic display element of the present invention has a transparent plate adhered to the outer surface of the substrate on the display side via an adhesive layer mainly composed of poly(meth)acrylic acid alkyl ester cured by ultraviolet rays. Because the pattern stands out and is visible on the surface of the transparent plate due to the refractive index effect, there are no shadows or blind spots even if the periphery of the element surface is hidden by an outer frame called an escutcheon, and the entire display area is visible. The visibility of the display is dramatically improved compared to conventional display elements that do not include the transparent plate. In addition, the adhesive layer in this display element has good transparency and does not contain bubbles, so it does not interfere with the color tone and display pattern of the display and background, and it also has excellent weather resistance and does not yellow over time. Since no deterioration or deterioration occurs, display quality can be maintained favorably over a long period of time.
以下、この発明の実施例を比較例と対比して説明する。 Examples of the present invention will be described below in comparison with comparative examples.
実施例１
縦３３鶴、横４６１１１Ｉ、厚さ１．１鰭の透明ガラス
からなる表示側基板の一面側に酸化インジウムを真空蒸
着して厚さ２．５００人の所定パターンの透明電極を形
成し、この電極上に酸化タングステンを真空蒸着して厚
さ５，０００人の所定パターンのエレクトロクロミック
物質層を形成して表示極とした。なお、この表示極のエ
レクトロクロミック物質層以外の表面にはＳｉｎｇを真
空蒸着して絶縁保護膜とした。Example 1 A transparent electrode with a predetermined pattern of 2.500 mm thick was formed by vacuum evaporating indium oxide on one side of a display side substrate made of transparent glass with a length of 33 cranes, a width of 46111 mm, and a thickness of 1.1 fins. Then, tungsten oxide was vacuum-deposited on the electrode to form an electrochromic material layer with a predetermined pattern of 5,000 layers thick to form a display electrode. Note that Sing was vacuum-deposited on the surface of the display electrode other than the electrochromic material layer to form an insulating protective film.
一方、縦２７鶴、横４４ｎ＋、厚さ１．１鶴の透明ガラ
スからなる対向側基板の一面側全面に酸化インジウムを
真空蒸着して厚さ２．５００人の電極を形成したのち、
この電極上にタングステン酸鉄１００重量部とカーボン
ペースト（徳力化学社製の商品名ＲＰ−１０）１００重
量部とからなる対極物質含有塗料を硬化後の厚みが２０
０μｍとなるように塗布したのち、２００℃にて４時間
加熱硬化させて対極物質層を形成して対向極とした。On the other hand, indium oxide was vacuum-deposited on the entire surface of one side of the opposing substrate, which was made of transparent glass and had a length of 27 squares, a width of 44 n+, and a thickness of 1.1 squares, to form an electrode with a thickness of 2.500 mm.
On this electrode, a paint containing a counter electrode substance consisting of 100 parts by weight of iron tungstate and 100 parts by weight of carbon paste (product name RP-10 manufactured by Tokuriki Chemical Co., Ltd.) was applied to a thickness of 20% after curing.
After coating to a thickness of 0 μm, the material was cured by heating at 200° C. for 4 hours to form a counter electrode material layer to serve as a counter electrode.
そして、上記側基板を表示極と対向極とが向かい合う形
で周辺部に厚さ５００μｍのガラス製方形環状スペーサ
を介挿して対向配置して接着剤にて固定するとともに、
その際上記両極間に酸化チタン１００重量部とポリテト
ラフルオロエチレン粉末１００重量部とからなるシート
状の前景材をはさみ込み、さらに１モル濃度のＬｉＣｌ
０ａを含むプロピレンカーボネートからなる電解液（比
抵抗６ Ｘ １０−’ΩＣｍ）０．３ｍｊ！を内部に封
入して表示セルを組み立てた。Then, the side substrates are arranged facing each other with a glass rectangular annular spacer having a thickness of 500 μm inserted around the periphery so that the display electrode and the counter electrode face each other, and are fixed with an adhesive.
At that time, a sheet-shaped foreground material consisting of 100 parts by weight of titanium oxide and 100 parts by weight of polytetrafluoroethylene powder was sandwiched between the above-mentioned two electrodes, and LiCl of 1 molar concentration was also sandwiched between the two electrodes.
Electrolytic solution made of propylene carbonate containing 0a (specific resistance 6 x 10-'ΩCm) 0.3mj! A display cell was assembled by enclosing it inside.
つぎに、この表示セルの表示側基板の外面にその周辺部
を除いて、全量中の７０重景％がアクリル酸ブチルから
なる紫外線硬化型接着剤をスクリーン印刷によって約１
０μｍ厚に塗布し、この塗布面上に縦２８龍、横４３鶴
、厚さ１．８ ｍ′ｍのガラス製透明板を密着させ、４
ＫＷの高圧水銀ランプを用いて２０ｃｍの距離から１分
間紫外線照射を行い、上記接着剤を硬化させた。さらに
リード端子の取付けと銀ペースト塗布による導電層の形
成を行い、第１図で示す構成のエレクトロクロミック表
示素子を作製した。Next, on the outer surface of the display side substrate of this display cell, excluding the peripheral area, an ultraviolet curing adhesive consisting of 70% of the total amount of butyl acrylate is applied by screen printing to approximately 100% of the outer surface of the display side substrate.
A transparent glass plate with a length of 28 dragons, a width of 43 cranes, and a thickness of 1.8 m was closely attached to the coated surface.
The adhesive was cured by irradiating ultraviolet light for 1 minute from a distance of 20 cm using a KW high-pressure mercury lamp. Further, lead terminals were attached and a conductive layer was formed by applying silver paste, thereby producing an electrochromic display element having the configuration shown in FIG. 1.
実施例２
紫外線硬化型接着剤として全量中の７０重量％がメタク
リル酸２−エチルヘキシルからなる接着剤を用いた以外
は、実施例１と同様にしてエレクトロクロミック表示素
子を作製した。Example 2 An electrochromic display element was produced in the same manner as in Example 1, except that an adhesive containing 2-ethylhexyl methacrylate at 70% by weight of the total amount was used as the ultraviolet curable adhesive.
比較例１
透明板の接着を行わなかった以外は実施例１と同様にし
てエレクトロクロミック表示素子を作製した。Comparative Example 1 An electrochromic display element was produced in the same manner as in Example 1 except that the transparent plate was not bonded.
比較例２
紫外線硬化型接着剤に代えてメチルメタアクリレート樹
脂を塩化メチレンに溶解した接着剤を用いて透明板の接
着を行った以外は、実施例１と同様にしてエレクトロク
ロミック表示素子を作製した。Comparative Example 2 An electrochromic display element was produced in the same manner as in Example 1, except that the transparent plate was bonded using an adhesive prepared by dissolving methyl methacrylate resin in methylene chloride instead of the ultraviolet curable adhesive. .
比較例３
紫外線硬化型接着剤として樹脂成分がエポキシアクリレ
ートを主体とした接着剤を用いた以外は、実施例１と同
様にしてエレクトロクロミック表示素子を作製した。Comparative Example 3 An electrochromic display element was produced in the same manner as in Example 1, except that an adhesive whose resin component was mainly epoxy acrylate was used as the ultraviolet curable adhesive.
比較例４
紫外線硬化型接着剤として樹脂成分がポリエステルアク
リレートを主体とした接着剤を用いた以外は、実施例１
と同様にしてエレクトロクロミック表示素子を作製した
。Comparative Example 4 Example 1 except that an adhesive whose resin component was mainly polyester acrylate was used as the ultraviolet curable adhesive.
An electrochromic display element was produced in the same manner as described above.
比較例５
紫外線硬化型接着剤として樹脂成分がポリウレタンアク
リレートを主体とした接着剤を用いた以外は、実施例１
と同様にしてエレクトロクロミック表示素子を作製した
。Comparative Example 5 Example 1 except that an adhesive whose resin component was mainly polyurethane acrylate was used as the ultraviolet curable adhesive.
An electrochromic display element was produced in the same manner as described above.
比較例６
紫外線硬化型接着剤として樹脂成分がポリエーテルアク
リレートを主体とした接着剤を用いた以外は、実施例１
と同様にしてエレクトロクロミック表示素子を作製した
。Comparative Example 6 Example 1 except that an adhesive whose resin component was mainly polyether acrylate was used as the ultraviolet curable adhesive.
An electrochromic display element was produced in the same manner as described above.
比較例７
紫外線硬化型接着剤として樹脂成分がメラミンアクリレ
ートを主体とした接着剤を用いた以外は、実施例１と同
様にしてエレクトロクロミック表示素子を作製した。Comparative Example 7 An electrochromic display element was produced in the same manner as in Example 1, except that an adhesive whose resin component was mainly melamine acrylate was used as the ultraviolet curable adhesive.
比較例８
紫外線硬化型接着剤として樹脂成分がシリコーンアクリ
レートを主体とした接着剤を用いた以外は、実施例１と
同様にしてエレクトロクロミック表示素子を作製した。Comparative Example 8 An electrochromic display element was produced in the same manner as in Example 1, except that an adhesive whose resin component was mainly silicone acrylate was used as the ultraviolet curable adhesive.
以上の実施例および比較例のエレクトロクロミック表示
素子をそれぞれ複数個用いて第３図の如き表示ボードを
作成し、外枠（エスカッション）による影および死角の
有無、表示の鮮明度、透明板表面への表示の浮き出しを
目視観察し、視認性を調べた。またこれら表示素子につ
いて、４５℃。A display board as shown in Fig. 3 was created using a plurality of the electrochromic display elements of the above examples and comparative examples, and the presence or absence of shadows and blind spots caused by the outer frame (escutcheon), the clarity of the display, and the transparent board surface. Visibility was examined by visually observing the embossed display. Furthermore, for these display elements, the temperature was 45°C.
９５％ＲＨの条件下で１００時間のウェザ−メーターテ
ストを行い、背景色（白）の色調変化によって耐候性を
調べた。これらの結果を下表に示す。A weather meter test was conducted for 100 hours under the condition of 95% RH, and the weather resistance was examined by changing the color tone of the background color (white). These results are shown in the table below.
なお、図中の○は良、△はやや良、×は不良を意味する
。In the figure, ◯ means good, △ means slightly good, and × means bad.
上記から明らかなように、この発明の表示素子は、外枠
（エスカッション）を取付けた場合の視認性が良好であ
り、しかも長期使用によっても表示品質の低下を生じな
いことが判る。これに対して、透明板が溶剤揮発型接着
剤にて接着された表示素子（比較例２）ではとくに接着
剤層の気泡によって表示の鮮明度が悪く、また透明板が
ポリ （メタ）アクリル酸アルキルエステル以外の紫外
線にて硬化された接着剤層を介して接着された表示素子
（比較例３〜８）ではとくに該接着剤層の耐候性に難が
あって長期使用によって色調変化をきたすことが判る。As is clear from the above, the display element of the present invention has good visibility when an outer frame (escutcheon) is attached, and furthermore, it can be seen that the display quality does not deteriorate even after long-term use. On the other hand, in a display element in which a transparent plate was bonded with a solvent-volatile adhesive (Comparative Example 2), the clarity of the display was particularly poor due to air bubbles in the adhesive layer, and the transparent plate was made of poly(meth)acrylic acid. Display elements bonded via adhesive layers other than alkyl esters cured by ultraviolet light (Comparative Examples 3 to 8) have particular problems with the weather resistance of the adhesive layer, causing color tone changes with long-term use. I understand.
第１図はこの発明のエレクトロクロミック表示素子の構
造例を示す縦断面図、第２図は従来の同表示素子の縦断
面図、第３図は同表示素子を用いた表示ボードの一部破
断正面図である。
１・・・表示側基板、４・・・表示極、５・・・対向側
基板、８・・・対向極、９・・・電解液、１７・・・透
明板、１８・・・接着剤層、１００・・・エレクトロク
ロミック表示素子
特許出願人 日立マクセル株式会社
第１図Fig. 1 is a vertical cross-sectional view showing an example of the structure of the electrochromic display element of the present invention, Fig. 2 is a longitudinal cross-sectional view of a conventional display element, and Fig. 3 is a partially broken view of a display board using the same display element. It is a front view. DESCRIPTION OF SYMBOLS 1... Display side substrate, 4... Display electrode, 5... Opposite side substrate, 8... Counter electrode, 9... Electrolyte solution, 17... Transparent plate, 18... Adhesive Layer, 100... Electrochromic display element patent applicant Hitachi Maxell Ltd. Figure 1
Claims (1)
向配置され、表示側の基板内面に形成された表示極と対
向側の基板内面に形成された対向極との間に電解液が封
入されてなるエレクトロクロミック表示素子において、
表示側の基板外面に透明板が紫外線にて硬化されたポリ
（メタ）アクリル酸アルキルエステルを主体とする接着
剤層を介して接着されていることを特徴とするエレクト
ロクロミック表示素子。(1) A pair of substrates with at least the display side being translucent are arranged facing each other, and an electrolyte is sealed between the display electrode formed on the inner surface of the substrate on the display side and the counter electrode formed on the inner surface of the substrate on the opposite side. In the electrochromic display element made of
An electrochromic display element characterized in that a transparent plate is adhered to the outer surface of a substrate on the display side via an adhesive layer mainly composed of poly(meth)acrylic acid alkyl ester cured by ultraviolet rays.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61063775A JPS62220932A (en) | 1986-03-20 | 1986-03-20 | Electrochromic display element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61063775A JPS62220932A (en) | 1986-03-20 | 1986-03-20 | Electrochromic display element |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62220932A true JPS62220932A (en) | 1987-09-29 |
Family
ID=13239081
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61063775A Pending JPS62220932A (en) | 1986-03-20 | 1986-03-20 | Electrochromic display element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62220932A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0602175A1 (en) * | 1991-09-04 | 1994-06-22 | Sun Active Glass Electrochrom | Electrochromic devices having refractive index-matched structure and methods of operating and manufacturing. |
| EP0676059A1 (en) * | 1992-12-24 | 1995-10-11 | Sun Active Glass Electrochromics, Inc. | Electrochromic devices |
| US5724177A (en) * | 1991-09-04 | 1998-03-03 | Sun Active Glass Electrochromics, Inc. | Electrochromic devices and methods |
| JP2012108552A (en) * | 2003-11-05 | 2012-06-07 | E Ink Corp | Electro-optic display |
| US9782949B2 (en) | 2008-05-30 | 2017-10-10 | Corning Incorporated | Glass laminated articles and layered articles |
| WO2018067030A1 (en) * | 2016-10-09 | 2018-04-12 | Сергей Анатольевич ДАВЫДЕНКО | Variable transparency element and variable transparency coating |
-
1986
- 1986-03-20 JP JP61063775A patent/JPS62220932A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0602175A1 (en) * | 1991-09-04 | 1994-06-22 | Sun Active Glass Electrochrom | Electrochromic devices having refractive index-matched structure and methods of operating and manufacturing. |
| EP0602175A4 (en) * | 1991-09-04 | 1994-12-14 | Sun Active Glass Electrochrom | Electrochromic devices having refractive index-matched structure and methods of operating and manufacturing. |
| US5724177A (en) * | 1991-09-04 | 1998-03-03 | Sun Active Glass Electrochromics, Inc. | Electrochromic devices and methods |
| US5757537A (en) * | 1991-09-04 | 1998-05-26 | Sun Active Glass Electrochromics, Inc. | Electrochromic devices and methods |
| EP0676059A1 (en) * | 1992-12-24 | 1995-10-11 | Sun Active Glass Electrochromics, Inc. | Electrochromic devices |
| EP0676059A4 (en) * | 1992-12-24 | 1995-11-29 | Sun Active Glass Electrochrom | Electrochromic devices. |
| JP2012108552A (en) * | 2003-11-05 | 2012-06-07 | E Ink Corp | Electro-optic display |
| US9782949B2 (en) | 2008-05-30 | 2017-10-10 | Corning Incorporated | Glass laminated articles and layered articles |
| WO2018067030A1 (en) * | 2016-10-09 | 2018-04-12 | Сергей Анатольевич ДАВЫДЕНКО | Variable transparency element and variable transparency coating |
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